US3506435A - Liquid-liquid extraction of reverberatory and converter slags by iron sulphide solutions - Google Patents

Liquid-liquid extraction of reverberatory and converter slags by iron sulphide solutions Download PDF

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Publication number
US3506435A
US3506435A US3506435DA US3506435A US 3506435 A US3506435 A US 3506435A US 3506435D A US3506435D A US 3506435DA US 3506435 A US3506435 A US 3506435A
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United States
Prior art keywords
slag
matte
copper
molten
liquid
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English (en)
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Nickolas J Themelis
Paul Spira
Frank Ajersch
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Noranda Inc
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Noranda Inc
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Assigned to NORANDA INC. reassignment NORANDA INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE DATE MAY 8, 1984 Assignors: NORANDA MINES LIMITED
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • This invention relates to a process for the recovery of non-ferrous metals from metallurgical slags.
  • the invention relates to the recovery of copper from copper containing iron silicate slags, such as blast furnace slags, converter slags, and reverberatory slags.
  • Matte smelting commonly used for extracting metals from sulphide ores is designed to gather the metal values to be extracted into a sulphide phase, known as the matte, which is produced simultaneously with an oxide slag rich in iron and silica.
  • the matte which is produced simultaneously with an oxide slag rich in iron and silica.
  • Oxides, silicates or sulphides of the non-ferrous metals become dissolved in the slag and small particles of sulphides become dispersed in the slag, resulting in appreciable losses of values in the slag.
  • the particles entrained in the slag are too small to settle out of the slag in a reasonable time.
  • Studies have also shown that a substantial fraction of the copper content in the slags produced during the smelting and converting of copper ores and concentrates is present as dissolved copper sulphide, the remainder being present as globules of matte.
  • a reverberatory slag with 0.40% copper may contain 0.20% copper as dissolved sulphide, while converter slag generally holds about 0.5% copper in solution.
  • the agitation is achieved with an inert gas or steam.
  • the agitation is achieved by injecting a reducing agent.
  • the principle of the process is basically one of reduction of oxidized metals in the slag, although the teachings indicate that the mere Patented Apr.
  • the sulphide compound should preferably 'be substantially free from those metals which are to be extracted from the slag.
  • Any matte can remove suspended matte in slag by Washing and collection, but the dissolved fraction of metal losses can only be extracted by consideration of the solubility equilibrium between the slag and matte.
  • Kalling includes as an essential requirement of his matte a certain amount of metallic iron.
  • each batch of slag shall be treated with at least one fresh charge of ferrous sulphide, a very complicated and time-consuming operation which could not possibly be carried out on a large scale.
  • the Kalling process could not possibly be used on a large scale, for example 3,000 tons per day of slag as contemplated in the present invention, except with a large number of cleaning vessels, due to the many matte charges to be handled. In the present process a single cleaning vessel can be worked on a very large scale.
  • Cu S copper sulphide
  • the figure demonstrates that, in order to decrease the copper content of a slag to a predetermined level, it is necessary to bring this slag into contact with matte of a copper content below a definite upper limit.
  • Diagrams similar to that shown in the figure can be established for other metals present in slag, and in particular, for nickel and cobalt.
  • the matte grade may be allowed to rise to as high as, for example, 30% copper before removing the matte from the extraction vessel. It will be seen from the figure that the last charge of slag to be cleaned will have a residual copper content slightly in excess of about 0.3%.
  • the slag to be treated by the liquid-liquid extraction process should preferably have a very low content of magnetite.
  • the magnetite content of the slag may be reduced in a separate vessel prior to liquid-liquid extraction or in the extraction vessel proper, either before or during the extraction process.
  • the liquid-liquid extraction can be performed simply by allowing the two liquids to stand in contact with each other.
  • the surface area of contact between the two liquids is quite small in relation to the total volume of material to be treated, the time required to reach equilibrium is considerable.
  • the extraction can be considerably speeded up by promoting liquid-liquid contact, for example by agitation of the molten bath.
  • said agitation may be achieved by any known means such as mechanical means, by stirring or by rocking, rotation, etc. of the vessel or furnace in which the extraction is being performed. Even simple pouring of one liquid into the other will promote liquid-liquid contact and so speed up the extraction.
  • the agitation is achieved by injecting into the molten mass through tuyeres or lances air or steam or an inert gas, e.g. nitrogen, or more preferably, a reducing gas.
  • a reducing gas such as a steam propane mixture
  • Pyrites can also be injected with any of the above gases while the agitation is being performed, for the purpose of reducing magnetite.
  • Any solid, liquid or gaseous reducing agent may be injected in a similar manner, for instance, mixtures of air or steam with pulverized coal or with fuel oil.
  • the melt After blowing or mechanical agitation, as the case may be, the melt is allowed to settle before separation of the two layers.
  • the whole extraction i.e. agitation and settling, can be performed within 20 to 30 minutes.
  • the agitation need only be performed for a few minutes, e.g. two to three minutes.
  • the temperature of the melt during extraction should be such as will produce a melt having a fluidity that will facilitate the mixing and separation of the two liquid phases. In general it may be stated that a temperature of about 225 F. is satisfactory.
  • the extraction process can be conducted in any convenient vessel or furnace.
  • the extraction is performed in a cylindrical tilting furnace, such as a Peirce-Smith converter.
  • the rotary furnace will be equipped with one or more oil or gas burners which maintain the bath in a molten state and provide a partially reducing or inert atmosphere, to prevent the excess formation of magnetite during the process.
  • the furnace is first charged with pyrites which is brought into the molten ferrous sulphide state.
  • a charge of slag for instance copper containing slag, is added and the total charge heated to about 2250 F.
  • Air or steam or a steam propane mixture or nitrogen is injected through suitably placed tuyeres or lances into the sulphide layer.
  • the blowing is continued for two to three minutes and then the melt is allowed to settle. After settling for 20 to 25 minutes, the slag layer is discharged.
  • a fresh charge of slag is then added and the blowing and settling repeated.
  • the half-hourly cycle can be repeated as many times as desired as the copper content of the ferrous sulphide layer gradually rises.
  • the process can be carried on until the content of the extracted metal, e.g. copper, in the sulphide layer rises to 10% or more, the exact value of the matte grade depending on the required extent of cleaning to be achieved in the slag. It may be necessary to add fresh pyrites to the bath at intervals to replace that converted to iron oxide by oxidation. The addition of pyrites may be done, for example, during the mixing period by injection through the lances or tuyeres with any of the gases that are used for agitating the bath. Eventually the sulphide layer can be discharged from the extraction vessel and processed to recover the copper in the conventional process which produced the slag.
  • the extracted metal e.g. copper
  • the pyrites may be smelted in a separate furnace to yield molten ferrous sulphide, said ferrous sulphide being subsequently transferred to the extraction vessel prior to adding any slag.
  • the extremely rapid rate of copper extraction provided by the process of the present invention permits the processing of large volumes of slag in relatively small furnaces, and this, coupled with an extremely high recovery of copper from the slag, renders the process of the invention extremely attractive from an economic point of view.
  • the following example is given.
  • one ladle (13 tons) of converter slag (Cu 0.93%, Si0 33.2%) was poured into a bath of matte in an oil-fired Peirce-Smith converter. Air was blown into the bath for five minutes at 6000 cu. ft. per min. Twenty minutes after blowing a sample of the bath showed 0.42% Cu. The matte analyzed at 26.1% Cu and 45.1% Fe.
  • This example further illustrates the rapid reduction of the' copper content of reverberatory slag by liquid-liquid contact of the' slag with low-grade copper matte.
  • the slag was separated from the matte and the matte was reused for treating a third charge of slag, which was cleaned to 0.23% Cu, at which point the matte grade was 12.9% Cu.
  • Six charges of slag were treated con secutively with the same matte in the manner described. At the end of the sixth cleaning cycle the matte grade was 22.5% and the slag was cleaned to 0.29% Cu.
  • one batch of matte was contacted successively, in the approximate ratio of 1 to 1 by weight, with ten batches of slag, each containing 1.4% Cu.
  • the matte initially contained 5% Cu and after the tenth cleaning cycle its copper content had increased to 28.9% while the slag was cleaned to 0.28% Cu.
  • four charges of reverberatory slag were cleaned from 0.31% to 0.12% Cu or less with one charge of very low-grade matte.
  • This example illustrates the distinguishing feature of the process of the invention, which consists in using one single charge of matte to clean successively many charges of slag.
  • a process for recovering a non-ferrous metal from molten iron silicate slag which comprises contacting successive slag charges with a single charge of a molten sulphide material selected from the group consisting of molten ferrous sulphide and a molten sulphide matte of the non-ferrous metal, each slag charge initially having a higher non-ferrous metal content than the non-ferrous metal content of the slag charge when in equilibrium with the charge of molten sulphide material, while maintaining the temperature of the molten sulphide material and the slag sufficiently high to produce a fluid melt which facilitates the mixing and subsequent separation of the slag and the molten sulphide material, thereby to reduce the non-ferrous metal content of the slag charge while increasing the non-ferrous metal content of the charge of molten sulphide material, separating each depleted slag charge from the charge of enriched molten 3.
  • a process as claimed in claim 1 in which a single charge of molten sulphide material is contacted with a series of slag charges until said molten sulphide material has a non-ferrous metal content at which it is substantially in equilibrium with a slag charge.
  • a process as claimed in claim 3 in which the agitating medium is selected from the class consisting of air, steam, a steam-propane mixture or nitrogen.
  • a process as claimed in claim 1 in which a series of slag charges is successively contacted with a single ferrous sulphide charge until said ferrous sulphide contains suflicient copper to reach a predetermined equilibrium value as between the copper content of said ferrous sulphide and said slag.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US3506435D 1966-04-15 1967-04-03 Liquid-liquid extraction of reverberatory and converter slags by iron sulphide solutions Expired - Lifetime US3506435A (en)

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Application Number Priority Date Filing Date Title
GB1659066A GB1176655A (en) 1966-04-15 1966-04-15 Liquid-Liquid Extraction of Reverberatory and Converter Slags by Iron Sulphide Solutions.

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US3506435D Expired - Lifetime US3506435A (en) 1966-04-15 1967-04-03 Liquid-liquid extraction of reverberatory and converter slags by iron sulphide solutions

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US (1) US3506435A (oth)
JP (1) JPS4829961B1 (oth)
BE (1) BE697000A (oth)
DE (1) DE1558425C2 (oth)
FI (1) FI49630C (oth)
GB (1) GB1176655A (oth)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1558425B1 (de) * 1966-04-15 1973-10-31 Noranda Mines Ltd Verfahren zur kontinuierlichen extraktion von kupfer aus geschmolzenen eisensilikatschlacken
US3857700A (en) * 1973-03-05 1974-12-31 Kennecott Copper Corp Pyrometallurgical recovery of copper values from converter slags
US3984235A (en) * 1973-01-10 1976-10-05 Boliden Aktiebolag Treatment of converter slag
US4032327A (en) * 1975-08-13 1977-06-28 Kennecott Copper Corporation Pyrometallurgical recovery of copper from slag material
US4717419A (en) * 1982-03-18 1988-01-05 Outokumpu Oy Method for treating iron-bearing slags containing precious metals, particularly slags created in the smelting process of copper and nickel
US4814004A (en) * 1987-05-29 1989-03-21 Falconbridge Limited Non-ferrous metal recovery
US9903005B2 (en) 2013-07-23 2018-02-27 Yanggu Xiangguang Copper Co., Ltd. Method and device for depleting copper smelting slag
US10265358B2 (en) 2015-06-19 2019-04-23 Qiuhong Wang Method for the preparation of medicated leaven massa by pure strain fermentation

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE7402163A0 (sv) * 1973-03-05 1974-09-06 Kennecott Copper Corp Förfarande och anordning för utvinning av ickejärnmetaller ur slagg
US4214897A (en) * 1978-01-13 1980-07-29 Metallurgie Hoboken Overpelt Process for the extraction of non-ferrous metals from slags and other metallurgical by-products
DE19960132A1 (de) * 1999-12-14 2001-06-21 Alexander Beckmann Verfahren zur Gewinnung von Kupfer und anderen Metallen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1231349A (en) * 1915-04-09 1917-06-26 James Brown Herreshoff Jr Process of treating slags.
US1544048A (en) * 1921-11-23 1925-06-30 Stout Harry Howard Treatment of copper metallurgical slag
US2035016A (en) * 1933-08-15 1936-03-24 Int Nickel Canada Smelting of ores
US2295219A (en) * 1940-05-10 1942-09-08 Kalling Bo Michael Sture Process for treating metallurgical slags
US2857263A (en) * 1955-10-15 1958-10-21 Noranda Mines Ltd Method for reducing metal losses in reverberatory furnace slag

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1822588A (en) * 1929-01-14 1931-09-08 United Verde Copper Company Recovering copper from slags
GB1176655A (en) * 1966-04-15 1970-01-07 Noranda Mines Ltd Liquid-Liquid Extraction of Reverberatory and Converter Slags by Iron Sulphide Solutions.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1231349A (en) * 1915-04-09 1917-06-26 James Brown Herreshoff Jr Process of treating slags.
US1544048A (en) * 1921-11-23 1925-06-30 Stout Harry Howard Treatment of copper metallurgical slag
US2035016A (en) * 1933-08-15 1936-03-24 Int Nickel Canada Smelting of ores
US2295219A (en) * 1940-05-10 1942-09-08 Kalling Bo Michael Sture Process for treating metallurgical slags
US2857263A (en) * 1955-10-15 1958-10-21 Noranda Mines Ltd Method for reducing metal losses in reverberatory furnace slag

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1558425B1 (de) * 1966-04-15 1973-10-31 Noranda Mines Ltd Verfahren zur kontinuierlichen extraktion von kupfer aus geschmolzenen eisensilikatschlacken
US3984235A (en) * 1973-01-10 1976-10-05 Boliden Aktiebolag Treatment of converter slag
US3857700A (en) * 1973-03-05 1974-12-31 Kennecott Copper Corp Pyrometallurgical recovery of copper values from converter slags
US4032327A (en) * 1975-08-13 1977-06-28 Kennecott Copper Corporation Pyrometallurgical recovery of copper from slag material
US4717419A (en) * 1982-03-18 1988-01-05 Outokumpu Oy Method for treating iron-bearing slags containing precious metals, particularly slags created in the smelting process of copper and nickel
US4814004A (en) * 1987-05-29 1989-03-21 Falconbridge Limited Non-ferrous metal recovery
GB2206606B (en) * 1987-05-29 1991-07-03 Falconbridge Ltd Non-ferrous metal recovery
US9903005B2 (en) 2013-07-23 2018-02-27 Yanggu Xiangguang Copper Co., Ltd. Method and device for depleting copper smelting slag
US10265358B2 (en) 2015-06-19 2019-04-23 Qiuhong Wang Method for the preparation of medicated leaven massa by pure strain fermentation

Also Published As

Publication number Publication date
DE1558425B1 (de) 1973-10-31
GB1176655A (en) 1970-01-07
JPS4829961B1 (oth) 1973-09-14
DE1558425C2 (de) 1974-05-30
BE697000A (oth) 1967-09-18
FI49630B (oth) 1975-04-30
FI49630C (fi) 1975-08-11

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Owner name: NORANDA INC.

Free format text: CHANGE OF NAME;ASSIGNOR:NORANDA MINES LIMITED;REEL/FRAME:004307/0376

Effective date: 19840504